It has been demonstrated that apart from the known compounds YbVO4 and Yb8V2O17, a substitutive solid solution is also formed in the binary oxide system V2O5-Yb2O3. This solid solution is characterized by limited solubility of vanadium(V) oxide in the crystal lattice of ytterbium oxide, and its general formula is Yb2-5x square 2xV3xO3, where 0.00 < x < 0.1667. The new solid solution was obtained from the mixtures of V2O5 and Yb2O3 oxides, containing vanadium(V) oxide in the amounts not exceeding 30 mol%, by high-energy ball milling in a planetary ball mill. The solid solution obtained was characterized using the methods XRD, DTA-TG, SEM, IR and UV-Vis-DR. It was found to crystallize in cubic system and to show a structure of Yb2O3. This solid solution was stable in air atmosphere at least up to similar to 800 degrees C, and the temperature of its decomposition decreased with increasing x, so with increasing degree of Yb3+ replacement with V5+ in the crystal lattice of Yb2O3. The energy gap estimated for this solid solution varied from similar to 2.5 eV for x = 0.0322 to similar to 2.6 eV for x = 0.1176, which means that this new solid solution is a semiconductor.